Green luminescent materials

ABSTRACT

There is provided a green luminescent material having Formula I or Formula II 
     
       
         
         
             
             
         
       
     
     R 1  and R 2  can be the same or different and can be hydrogen, alkoxy, tertiary alkyl, or cycloalkyl. R 3  and R 4  are the same or different and can be fluorine, aryl, or alkyl. There is also provided an organic electronic device containing the green luminescent material.

RELATED APPLICATION DATA

This application claims priority under 35 U.S.C. § 119(e) from U.S.Provisional Application No. 60/941,380 filed on Jun. 1, 2007, which isincorporated by reference herein in its entirety.

BACKGROUND INFORMATION

1. Field of the Disclosure

This disclosure relates in general to green luminescent materials andtheir synthesis.

2. Description of the Related Art

Organic electronic devices that emit light, such as light-emittingdiodes that make up displays, are present in many different kinds ofelectronic equipment. In all such devices, an organic active layer issandwiched between two electrical contact layers. At least one of theelectrical contact layers is light-transmitting so that light can passthrough the electrical contact layer. The organic active layer emitslight through the light-transmitting electrical contact layer uponapplication of electricity across the electrical contact layers.

It is well known to use organic electroluminescent compounds as theactive component in light-emitting diodes. Simple organic molecules,such as anthracene, thiadiazole derivatives, and coumarin derivativesare known to show electroluminescence. In some cases these smallmolecule materials are present as a dopant in a host material to improveprocessing and/or electronic properties.

There is a continuing need for new emissive materials, especially forluminescent compounds that are green-emitting.

SUMMARY

There is provided a green luminescent material having Formula I orFormula II

wherein:

R¹ and R² are the same or different and are selected from the groupconsisting of hydrogen, alkoxy, tertiary alkyl, and cycloalkyl; and

-   -   R³ and R⁴ are the same or different and are selected from the        group consisting of fluorine, aryl and alkyl.

In some embodiments, at least one of R¹ and R² is not hydrogen.

There is also provided an organic electronic device comprising a firstelectrical contact, a second electrical contact and a photoactive layertherebetween, the photoactive layer comprising the above greenluminescent material.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 includes an illustration of one example of an organiclight-emitting diode.

Skilled artisans appreciate that objects in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the objects in the figures may beexaggerated relative to other objects to help to improve understandingof embodiments.

DETAILED DESCRIPTION

Many aspects and embodiments are described herein and are merelyexemplary and not limiting. After reading this specification, skilledartisans will appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims. The detailed description first addresses Definitions andClarification of Terms followed by the Green Luminescent Materials,Synthesis, Devices, and finally Examples.

1. DEFINITIONS AND CLARIFICATION OF TERMS

Before addressing details of embodiments described below, some terms aredefined or clarified.

The term “alkoxy” is intended to mean a group having the formula —OR,which is attached via the oxygen, where R is an alkyl.

The term “alkyl” is intended to mean a group derived from an aliphatichydrocarbon and includes a linear, a branched, or a cyclic group. Insome embodiments, an alkyl has from 1-20 carbon atoms.

The term “cycloalkyl” is intended to mean an alkyl group having one ormore ring structures. In some embodiments, a cycloalkyl has from 4-20carbon atoms.

The term “secondary alkyl” is intended to mean an alkyl group whichincludes a secondary carbon. In some embodiments, a secondary alkyl hasfrom 3-20 carbon atoms. The term “secondary carbon” is intended to meana carbon linked to two additional carbons.

The term “tertiary alkyl” is intended to mean an alkyl group whichincludes a tertiary carbon. In some embodiments, a tertiary alkyl hasfrom 4-20 carbon atoms. The term “tertiary carbon” is intended to mean acarbon linked to three additional carbons.

The term “aryl” is intended to mean a group derived from an aromatichydrocarbon. The group may include one or more aromatic rings.

The terms “luminescent material” and “emitter” are intended to mean amaterial that emits light when activated by an applied voltage (such asin a light-emitting diode or light-emitting electrochemical cell).

The term “green luminescent material” is intended to mean a materialcapable of emitting radiation that has an emission maximum at awavelength in a range of approximately 500-600 nm.

The term “layer” is used interchangeably with the term “film” and refersto a coating covering a desired area. The term is not limited by size.The area can be as large as an entire device or as small as a specificfunctional area such as the actual visual display, or as small as asingle sub-pixel. Layers and films can be formed by any conventionaldeposition technique, including vapor deposition, liquid deposition(continuous and discontinuous techniques), and thermal transfer.Continuous deposition techniques, include but are not limited to, spincoating, gravure coating, curtain coating, dip coating, slot-diecoating, spray coating, and continuous nozzle coating. Discontinuousdeposition techniques include, but are not limited to, ink jet printing,gravure printing, and screen printing.

The term “organic electronic device” or sometimes just “electronicdevice” is intended to mean a device including one or more organicsemiconductor layers or materials.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in textbooks and other sources within the organic light-emittingdiode display, photodetector, photovoltaic, and semiconductive memberarts.

2. GREEN LUMINESCENT MATERIALS

The new green luminescent materials described herein have Formula I orFormula II

wherein:

R¹ and R² are the same or different and are selected from the groupconsisting of hydrogen, alkoxy, tertiary alkyl, and cycloalkyl.

R³ and R⁴ are the same or different and are selected from the groupconsisting of fluorine, aryl and alkyl.

In some embodiments, the alkoxy group has from 1-10 carbon atoms; insome embodiments, 1-5 carbons. Examples of suitable alkoxy groupsinclude, but are not limited to, methoxy and ethoxy groups.

In some embodiments, the tertiary alkyl group has from 4-12 carbonatoms; in some embodiments, 4-6 carbons. Examples of suitable tertiaryalkyl groups include, but are not limited to, tertiary butyl andneopentyl groups.

In some embodiments, the cycloalkyl group has from 6-20 carbon atoms; insome embodiments, 6-12. Examples of suitable cycloalkyl groups include,but are not limited to, cyclohexyl, 1-methylcyclohexyl, and 1-adamantylgroups.

In some embodiments, R¹ and R² are the same.

In some embodiments, at least one of R³ and R⁴ is a secondary alkyl or atertiary alkyl. In some embodiments, at least one of R3 and R4 is anaryl group. In some embodiments, the aryl group is selected from phenyl,naphthyl, biphenyl, and terphenyl groups. In some embodiments R³ and R⁴are the same.

Examples of green luminescent materials having Formula I or Formula IIinclude, but are not limited to, compounds G1 through G12 in Table 1below:

TABLE 1 Green Luminescent Compounds Compound Formula R¹ R² R³ R⁴ G1 I HH i-propyl t-butyl G2 I t-butyl H i-propyl t-butyl G3 I t-butyl t-butyli-propyl t-butyl G4 I 1-methylcyclohexyl 1-methylcyclohexyl i-propylt-butyl G5 II 1-methylcyclohexyl 1-methylcyclohexyl i-propyl t-butyl G6I methoxy methoxy i-propyl t-butyl G7 I 1-adamantyl 1-adamantyl i-propylt-butyl G8 II 1-adamantyl 1-adamantyl i-propyl t-butyl G9 I t-butylt-butyl F F G10 I 1-adamantyl 1-adamantyl phenyl phenyl G11 I1-adamantyl 1-adamantyl t-butyl 3-biphenyl G12 I 1-adamantyl 1-adamantylt-butyl phenyl

3. SYNTHESIS

The green luminescent materials described herein, are generally preparedaccording to the following scheme:

When R¹═R², the first step involved alkylation of anthracene usingFriedel Crafts chemistry with the appropriate alcohol, for example,t-butanol, 1-adamantanol or 1-methylcyclohexanol. This can be carriedout in a solvent such as neat trifluoroacetic acid, generally withheating, followed by isolation and chromatographic purification. Forsome of the compounds, the substituted anthracene is commerciallyavailable, such as 2-t-butylanthracene.

The substituted anthracene can then be brominated, such as by using Br₂in CCl₄. For compounds where R¹═R²═H, the dibromide is commerciallyavailable.

The brominated product is then reacted with the appropriate secondaryamine with a Pd catalyst. The secondary amine can also be prepared by Pdcatalyzed amination.

In cases where the substituent is an alkoxy group, the substitutedanthracene intermediate can be prepared by etherification ofdihydroxyanthroquinone, followed by hydride reduction.

In many cases, mixtures of the compounds having Formula I and Formula IIare formed. The compounds can be separated or used as a mixture,depending upon the physical properties.

4. DEVICES

Organic electronic devices that may benefit from having one or morelayers comprising the green luminescent materials described hereininclude, but are not limited to, (1) devices that convert electricalenergy into radiation (e.g., a light-emitting diode, light emittingdiode display, or diode laser), (2) devices that detect signals throughelectronics processes (e.g., photodetectors, photoconductive cells,photoresistors, photoswitches, phototransistors, phototubes, IRdetectors), (3) devices that convert radiation into electrical energy,(e.g., a photovoltaic device or solar cell), and (4) devices thatinclude one or more electronic components that include one or moreorganic semi-conductor layers (e.g., a transistor or diode).

One illustration of an organic electronic device structure is shown inFIG. 1. The device 100 has a first electrical contact layer, an anodelayer 110 and a second electrical contact layer, a cathode layer 160,and a photoactive layer 140 between them. Adjacent to the anode is abuffer layer 120. Adjacent to the buffer layer is a hole transport layer130, comprising hole transport material. Adjacent to the cathode may bean electron transport layer 150, comprising an electron transportmaterial. As an option, devices may use one or more additional holeinjection or hole transport layers (not shown) next to the anode 110and/or one or more additional electron injection or electron transportlayers (not shown) next to the cathode 160.

In one embodiment, the different layers have the following range ofthicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000 Å;buffer layer 120, 50-2000 Å, in one embodiment 200-1000 Å; holetransport layer 120, 50-2000 Å, in one embodiment 200-1000 Å;photoactive layer 130, 10-2000 Å, in one embodiment 100-1000 Å; layer140, 50-2000 Å, in one embodiment 100-1000 Å; cathode 150, 200-10000 Å,in one embodiment 300-5000 Å. The location of the electron-holerecombination zone in the device, and thus the emission spectrum of thedevice, can be affected by the relative thickness of each layer. Thedesired ratio of layer thicknesses will depend on the exact nature ofthe materials used.

a. Photoactive Layer

The green luminescent materials described herein are particularly suitedas the photoactive material in the photoactive layer 140. They can beused alone, in combination with other luminescent materials, or in ahost material.

In some embodiments, the host is a bis-condensed cyclic aromaticcompound.

In some embodiments, the host is an anthracene derivative compound. Insome embodiments the compound has the formula:

An-L-An

where:

An is an anthracene moiety;

L is a divalent connecting group.

In some embodiments of this formula, L is a single bond, —O—, —S—,—N(R)—, or an aromatic group. In some embodiments, An is a mono- ordiphenylanthryl moiety.

In some embodiments, the host has the formula:

A-An-A

where:

An is an anthracene moiety;

A is an aromatic group.

In some embodiments, the host is a diarylanthracene. In some embodimentsthe compound is symmetrical and in some embodiments the compound isnon-symmetrical.

In some embodiments, the host has the formula:

where:

A¹ and A² are the same or different at each occurrence and are selectedfrom the group consisting of H, an aromatic group, and an alkenyl group,or A may represent one or more fused aromatic rings;

p and q are the same or different and are an integer from 1-3. In someembodiments, the anthracene derivative is non-symmetrical. In someembodiments, p=2 and q=1. In some embodiments, at least one of A¹ and A²is a naphthyl group.

In some embodiments, the host is selected from the group consisting of

and combinations thereof.b. Other Device Layers

The other layers in the device can be made of any materials which areknown to be useful in such layers.

The anode 110 is an electrode that is particularly efficient forinjecting positive charge carriers. It can be made of, for examplematerials containing a metal, mixed metal, alloy, metal oxide ormixed-metal oxide, or it can be a conducting polymer, and mixturesthereof. Suitable metals include the Group 11 metals, the metals inGroups 4, 5, and 6, and the Group 8-10 transition metals. If the anodeis to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14metals, such as indium-tin-oxide, are generally used. The anode may alsocomprise an organic material such as polyaniline as described in“Flexible light-emitting diodes made from soluble conducting polymer,”Nature vol. 357, pp 477 479 (11 Jun. 1992). At least one of the anodeand cathode should be at least partially transparent to allow thegenerated light to be observed.

The buffer layer 120 comprises buffer material and may have one or morefunctions in an organic electronic device, including but not limited to,planarization of the underlying layer, charge transport and/or chargeinjection properties, scavenging of impurities such as oxygen or metalions, and other aspects to facilitate or to improve the performance ofthe organic electronic device The buffer layer can be formed withpolymeric materials, such as polyaniline (PANI) orpolyethylenedioxythiophene (PEDOT), which are often doped with protonicacids. The protonic acids can be, for example, poly(styrenesulfonicacid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and the like.

The buffer layer can comprise charge transfer compounds, and the like,such as copper phthalocyanine and thetetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ).

In some embodiments, the buffer layer comprises at least oneelectrically conductive polymer and at least one fluorinated acidpolymer.

In some embodiments, the electrically conductive polymer will form afilm which has a conductivity of at least 10⁻⁷ S/cm. The monomer fromwhich the conductive polymer is formed, is referred to as a “precursormonomer”. A copolymer will have more than one precursor monomer. In someembodiments, the conductive polymer is made from at least one precursormonomer selected from thiophenes, selenophenes, tellurophenes, pyrroles,anilines, and polycyclic aromatics. The polymers made from thesemonomers are referred to herein as polythiophenes, poly(selenophenes),poly(tellurophenes), polypyrroles, polyanilines, and polycyclic aromaticpolymers, respectively. The term “polycyclic aromatic” refers tocompounds having more than one aromatic ring. The rings may be joined byone or more bonds, or they may be fused together. The term “aromaticring” is intended to include heteroaromatic rings. A “polycyclicheteroaromatic” compound has at least one heteroaromatic ring. In someembodiments, the polycyclic aromatic polymers arepoly(thienothiophenes).

The fluorinated acid polymer can be any polymer which is fluorinated andhas acidic groups with acidic protons. The term includes partially andfully fluorinated materials. In some embodiments, the fluorinated acidpolymer is highly fluorinated. The term “highly fluorinated” means thatat least 50% of the available hydrogens bonded to a carbon, have beenreplaced with fluorine. The acidic groups supply an ionizable proton. Insome embodiments, the acidic proton has a pKa of less than 3. In someembodiments, the acidic proton has a pKa of less than 0. In someembodiments, the acidic proton has a pKa of less than −5. The acidicgroup can be attached directly to the polymer backbone, or it can beattached to side chains on the polymer backbone. Examples of acidicgroups include, but are not limited to, carboxylic acid groups, sulfonicacid groups, sulfonimide groups, phosphoric acid groups, phosphonic acidgroups, and combinations thereof. The acidic groups can all be the same,or the polymer may have more than one type of acidic group.

In some embodiments the fluorinated acid polymer is water-soluble. Insome embodiments, the fluorinated acid polymer is dispersible in water.In some embodiments, the fluorinated acid polymer is organic solventwettable.

In some embodiments, fluorinated acid polymer has a polymer backbonewhich is fluorinated. Examples of suitable polymeric backbones include,but are not limited to, polyolefins, polyacrylates, polymethacrylates,polyimides, polyamides, polyaramids, polyacrylamides, polystyrenes, andcopolymers thereof. In some embodiments, the polymer backbone is highlyfluorinated. In some embodiments, the polymer backbone is fullyfluorinated.

In some embodiments, the acidic groups are sulfonic acid groups orsulfonimide groups. A sulfonimide group has the formula:

—SO₂—NH—SO₂—R

where R is an alkyl group.

In some embodiments, the acidic groups are on a fluorinated side chain.In some embodiments, the fluorinated side chains are selected from alkylgroups, alkoxy groups, amido groups, ether groups, and combinationsthereof.

In some embodiments, the fluorinated acid polymer has a fluorinatedolefin backbone, with pendant fluorinated ether sulfonate, fluorinatedester sulfonate, or fluorinated ether sulfonimide groups. In someembodiments, the polymer is a copolymer of 1,1-difluoroethylene and2-(1,1-difluoro-2-(trifluoromethyl)allyloxy)-1,1,2,2-tetrafluoroethanesulfonicacid. In some embodiments, the polymer is a copolymer of ethylene and2-(2-(1,2,2-trifluorovinyloxy)-1,1,2,3,3,3-hexafluoropropoxy)-1,1,2,2-tetrafluoroethanesulfonicacid. These copolymers can be made as the corresponding sulfonylfluoride polymer and then can be converted to the sulfonic acid form.

In some embodiments, the fluorinated acid polymer is homopolymer orcopolymer of a fluorinated and partially sulfonated poly(arylene ethersulfone). The copolymer can be a block copolymer. Examples of comonomersinclude, but are not limited to butadiene, butylene, isobutylene,styrene, and combinations thereof.

In some embodiments, the buffer layer is made from an aqueous dispersionof an electrically conducting polymer and a colloid-forming polymericacid. Such materials have been described in, for example, published U.S.patent applications 2004-0102577, 2004-0127637, and 2005-0205860.

The hole transport layer 130 is a layer which facilitates migration ofpositive charges through the thickness of the layer with relativeefficiency and small loss of charge. Examples of hole transportmaterials for the hole transport layer have been summarized for example,in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol.18, p. 837-860, 1996, by Y. Wang. Both hole transporting small moleculesand polymers can be used. Commonly used hole transporting moleculesinclude, but are not limited to:4,4′,4″-tris(N,N-diphenyl-amino)-triphenylamine (TDATA);4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA);N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD); 4,4′-bis(carbazol-9-yl)biphenyl (CBP);1,3-bis(carbazol-9-yl)benzene (mCP);1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC);N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD); tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA);α-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehydediphenylhydrazone (DEH); triphenylamine (TPA);bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP);1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB);N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB);N,N′-bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB); andporphyrinic compounds, such as copper phthalocyanine. Commonly used holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes),polyanilines, and polypyrroles. It is also possible to obtain holetransporting polymers by doping hole transporting molecules such asthose mentioned above into polymers such as polystyrene andpolycarbonate.

In some embodiments, the hole transport layer comprises a hole transportpolymer. In some embodiments, the hole transport polymer is adistyrylaryl compound. In some embodiments, the aryl group is has two ormore fused aromatic rings. In some embodiments, the aryl group is anacene. The term “acene” as used herein refers to a hydrocarbon parentcomponent that contains two or more ortho-fused benzene rings in astraight linear arrangement.

In some embodiments, the hole transport polymer is an arylamine polymer.In some embodiments, it is a copolymer of fluorene and arylaminemonomers.

In some embodiments, the polymer has crosslinkable groups. In someembodiments, crosslinking can be accomplished by a heat treatment and/orexposure to UV or visible radiation. Examples of crosslinkable groupsinclude, but are not limited to vinyl, acrylate, perfluorovinylether,1-benzo-3,4-cyclobutane, siloxane, and methyl esters. Crosslinkablepolymers can have advantages in the fabrication of solution-processOLEDs. The application of a soluble polymeric material to form a layerwhich can be converted into an insoluble film subsequent to deposition,can allow for the fabrication of multilayer solution-processed OLEDdevices free of layer dissolution problems.

Examples of crosslinkable polymers can be found in, for example,published US patent application 2005-0184287 and published PCTapplication WO 2005/052027.

In some embodiments, the hole transport layer comprises a polymer whichis a copolymer of 9,9-dialkylfluorene and triphenylamine. In someembodiments, the polymer is a copolymer of 9,9-dialkylfluorene and4,4′-bis(diphenylamino)biphenyl. In some embodiments, the polymer is acopolymer of 9,9-dialkylfluorene and TPB. In some embodiments, thepolymer is a copolymer of 9,9-dialkylfluorene and NPB. In someembodiments, the copolymer is made from a third comonomer selected from(vinylphenyl)diphenylamine and 9,9-distyrylfluorene or9,9-di(vinylbenzyl)fluorene. In some embodiments, the hole transportmaterial can be admixed with an electron acceptor material or anelectron donor material.

The electron transport layer 150 is a layer which facilitates migrationof negative charges through the thickness of the layer with relativeefficiency and small loss of charge. Examples of electron transportmaterials which can be used in the optional electron transport layer140, include metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (AlQ),bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum (BAlq),tetrakis-(8-hydroxyquinolato)hafnium (HfQ) andtetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds suchas 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivativessuch as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthrolines such as4,7-diphenyl-1,10-phenanthroline (DPA) or further substituted versionsof DPA, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); andmixtures thereof. In some embodiments, the electron transport materialcan be admixed with an electron acceptor material or an electron donormaterial.

The cathode 160, is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode can be anymetal or nonmetal having a lower work function than the anode. Materialsfor the cathode can be selected from alkali metals of Group 1 (e.g., Li,Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, includingthe rare earth elements and lanthanides, and the actinides. Materialssuch as aluminum, indium, calcium, barium, samarium and magnesium, aswell as combinations, can be used. Li- and Cs-containing organometalliccompounds, LiF, Li₂O, and CsF can also be deposited between the organiclayer 150 and the cathode layer 160 to lower the operating voltage. Thislayer, not shown, may be referred to as an electron injection layer.

c. Device Fabrication

The device layers can be formed by any deposition technique, orcombinations of techniques, including vapor deposition, liquiddeposition, and thermal transfer.

In some embodiments, the device is fabricated by liquid deposition ofthe buffer layer, the hole transport layer, and the photoactive layer,and by vapor deposition of the anode, the electron transport layer, anelectron injection layer and the cathode.

The buffer layer can be deposited from any liquid medium in which it isdissolved or dispersed and from which it will form a film. In oneembodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is selected from the group consisting of alcohols,ketones, cyclic ethers, and polyols. In one embodiment, the organicliquid is selected from dimethylacetamide (“DMAc”), N-methylpyrrolidone(“NMP”), dimethylformamide (“DMF”), ethylene glycol (“EG”), aliphaticalcohols, and mixtures thereof. The buffer material can be present inthe liquid medium in an amount from 0.5 to 10 percent by weight. Otherweight percentages of buffer material may be used depending upon theliquid medium. The buffer layer can be applied by any continuous ordiscontinuous liquid deposition technique. In one embodiment, the bufferlayer is applied by spin coating. In one embodiment, the buffer layer isapplied by ink jet printing. After liquid deposition, the liquid mediumcan be removed in air, in an inert atmosphere, or by vacuum, at roomtemperature or with heating. In one embodiment, the layer is heated to atemperature less than 275° C. In one embodiment, the heating temperatureis between 100° C. and 275° C. In one embodiment, the heatingtemperature is between 100° C. and 120° C. In one embodiment, theheating temperature is between 120° C. and 140° C. In one embodiment,the heating temperature is between 140° C. and 160° C. In oneembodiment, the heating temperature is between 160° C. and 180° C. Inone embodiment, the heating temperature is between 180° C. and 200° C.In one embodiment, the heating temperature is between 200° C. and 220°C. In one embodiment, the heating temperature is between 190° C. and220° C. In one embodiment, the heating temperature is between 220° C.and 240° C. In one embodiment, the heating temperature is between 240°C. and 260° C. In one embodiment, the heating temperature is between260° C. and 275° C. The heating time is dependent upon the temperature,and is generally between 5 and 60 minutes. In one embodiment, the finallayer thickness is between 5 and 200 nm. In one embodiment, the finallayer thickness is between 5 and 40 nm. In one embodiment, the finallayer thickness is between 40 and 80 nm. In one embodiment, the finallayer thickness is between 80 and 120 nm. In one embodiment, the finallayer thickness is between 120 and 160 nm. In one embodiment, the finallayer thickness is between 160 and 200 nm.

The hole transport layer can be deposited from any liquid medium inwhich it is dissolved or dispersed and from which it will form a film.In one embodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is an aromatic solvent. In one embodiment, theorganic liquid is selected from chloroform, dichloromethane, toluene,xylene, mesitylene, anisole, and mixtures thereof. The hole transportmaterial can be present in the liquid medium in a concentration of 0.2to 2 percent by weight. Other weight percentages of hole transportmaterial may be used depending upon the liquid medium. The holetransport layer can be applied by any continuous or discontinuous liquiddeposition technique. In one embodiment, the hole transport layer isapplied by spin coating. In one embodiment, the hole transport layer isapplied by ink jet printing. After liquid deposition, the liquid mediumcan be removed in air, in an inert atmosphere, or by vacuum, at roomtemperature or with heating. In one embodiment, the layer is heated to atemperature of 300° C. or less. In one embodiment, the heatingtemperature is between 170° C. and 275° C. In one embodiment, theheating temperature is between 170° C. and 200° C. In one embodiment,the heating temperature is between 190° C. and 220° C. In oneembodiment, the heating temperature is between 210° C. and 240° C. Inone embodiment, the heating temperature is between 230° C. and 270° C.In one embodiment, the heating temperature is between 270° C. and 300°C. The heating time is dependent upon the temperature, and is generallybetween 5 and 60 minutes. In one embodiment, the final layer thicknessis between 5 and 50 nm. In one embodiment, the final layer thickness isbetween 5 and 15 nm. In one embodiment, the final layer thickness isbetween 15 and 25 nm. In one embodiment, the final layer thickness isbetween 25 and 35 nm. In one embodiment, the final layer thickness isbetween 35 and 50 nm.

The photoactive layer can be deposited from any liquid medium in whichit is dissolved or dispersed and from which it will form a film. In oneembodiment, the liquid medium consists essentially of one or moreorganic solvents. In one embodiment, the liquid medium consistsessentially of water or water and an organic solvent. In one embodimentthe organic solvent is an aromatic solvent. In one embodiment, theorganic solvent is selected from chloroform, dichloromethane, toluene,anisole, 2-butanone, 3-pentanone, butyl acetate, acetone, xylene,mesitylene, chlorobenzene, tetrahydrofuran, diethyl ether,trifluorotoluene, and mixtures thereof. The photoactive material can bepresent in the liquid medium in a concentration of 0.2 to 2 percent byweight. Other weight percentages of photoactive material may be useddepending upon the liquid medium. The photoactive layer can be appliedby any continuous or discontinuous liquid deposition technique. In oneembodiment, the photoactive layer is applied by spin coating. In oneembodiment, the photoactive layer is applied by ink jet printing. Afterliquid deposition, the liquid medium can be removed in air, in an inertatmosphere, or by vacuum, at room temperature or with heating. Optimalbaking conditions depend on the vapor pressure properties of the liquidsbeing removed and their molecular interaction with the liquids. In oneembodiment, the deposited layer is heated to a temperature that isgreater than the Tg of the material having the highest Tg. In oneembodiment, the deposited layer is heated between 10 and 20° C. higherthan the Tg of the material having the highest Tg. In one embodiment,the deposited layer is heated to a temperature that is less than the Tgof the material having the lowest Tg. In one embodiment, the heatingtemperature is at least 10° C. less than the lowest Tg. In oneembodiment, the heating temperature is at least 20° C. less than thelowest Tg. In one embodiment, the heating temperature is at least 30° C.less than the lowest Tg. In one embodiment, the heating temperature isbetween 50° C. and 150° C. In one embodiment, the heating temperature isbetween 50° C. and 75° C. In one embodiment, the heating temperature isbetween 75° C. and 100° C. In one embodiment, the heating temperature isbetween 100° C. and 125° C. In one embodiment, the heating temperatureis between 125° C. and 150° C. The heating time is dependent upon thetemperature, and is generally between 5 and 60 minutes. In oneembodiment, the final layer thickness is between 25 and 100 nm. In oneembodiment, the final layer thickness is between 25 and 40 nm. In oneembodiment, the final layer thickness is between 40 and 65 nm. In oneembodiment, the final layer thickness is between 65 and 80 nm. In oneembodiment, the final layer thickness is between 80 and 100 nm.

The electron transport layer can be deposited by any vapor depositionmethod. In one embodiment, it is deposited by thermal evaporation undervacuum. In one embodiment, the final layer thickness is between 1 and100 nm. In one embodiment, the final layer thickness is between 1 and 15nm. In one embodiment, the final layer thickness is between 15 and 30nm. In one embodiment, the final layer thickness is between 30 and 45nm. In one embodiment, the final layer thickness is between 45 and 60nm. In one embodiment, the final layer thickness is between 60 and 75nm. In one embodiment, the final layer thickness is between 75 and 90nm. In one embodiment, the final layer thickness is between 90 and 100nm.

The electron injection layer can be deposited by any vapor depositionmethod. In one embodiment, it is deposited by thermal evaporation undervacuum. In one embodiment, the vacuum is less than 10⁻⁶ torr. In oneembodiment, the vacuum is less than 10⁻⁷ torr. In one embodiment, thevacuum is less than 10⁻⁸ torr. In one embodiment, the material is heatedto a temperature in the range of 100° C. to 400° C.; 150° C. to 350° C.preferably. The vapor deposition rates given herein are in units ofAngstroms per second. In one embodiment, the material is deposited at arate of 0.5 to 10 Å/sec. In one embodiment, the material is deposited ata rate of 0.5 to 1 Å/sec. In one embodiment, the material is depositedat a rate of 1 to 2 Å/sec. In one embodiment, the material is depositedat a rate of 2 to 3 Å/sec. In one embodiment, the material is depositedat a rate of 3 to 4 Å/sec. In one embodiment, the material is depositedat a rate of 4 to 5 Å/sec. In one embodiment, the material is depositedat a rate of 5 to 6 Å/sec. In one embodiment, the material is depositedat a rate of 6 to 7 Å/sec. In one embodiment, the material is depositedat a rate of 7 to 8 Å/sec. In one embodiment, the material is depositedat a rate of 8 to 9 Å/sec. In one embodiment, the material is depositedat a rate of 9 to 10 Å/sec. In one embodiment, the final layer thicknessis between 0.1 and 3 nm. In one embodiment, the final layer thickness isbetween 0.1 and 1 nm. In one embodiment, the final layer thickness isbetween 1 and 2 nm. In one embodiment, the final layer thickness isbetween 2 and 3 nm.

The cathode can be deposited by any vapor deposition method. In oneembodiment, it is deposited by thermal evaporation under vacuum. In oneembodiment, the vacuum is less than 10⁻⁶ torr. In one embodiment, thevacuum is less than 10⁻⁷ torr. In one embodiment, the vacuum is lessthan 10⁻⁸ torr. In one embodiment, the material is heated to atemperature in the range of 100° C. to 400° C.; 150° C. to 350° C.preferably. In one embodiment, the material is deposited at a rate of0.5 to 10 Å/sec. In one embodiment, the material is deposited at a rateof 0.5 to 1 Å/sec. In one embodiment, the material is deposited at arate of 1 to 2 Å/sec. In one embodiment, the material is deposited at arate of 2 to 3 Å/sec. In one embodiment, the material is deposited at arate of 3 to 4 Å/sec. In one embodiment, the material is deposited at arate of 4 to 5 Å/sec. In one embodiment, the material is deposited at arate of 5 to 6 Å/sec. In one embodiment, the material is deposited at arate of 6 to 7 Å/sec. In one embodiment, the material is deposited at arate of 7 to 8 Å/sec. In one embodiment, the material is deposited at arate of 8 to 9 Å/sec. In one embodiment, the material is deposited at arate of 9 to 10 Å/sec. In one embodiment, the final layer thickness isbetween 10 and 10000 nm. In one embodiment, the final layer thickness isbetween 10 and 1000 nm. In one embodiment, the final layer thickness isbetween 10 and 50 nm. In one embodiment, the final layer thickness isbetween 50 and 100 nm. In one embodiment, the final layer thickness isbetween 100 and 200 nm. In one embodiment, the final layer thickness isbetween 200 and 300 nm. In one embodiment, the final layer thickness isbetween 300 and 400 nm. In one embodiment, the final layer thickness isbetween 400 and 500 nm. In one embodiment, the final layer thickness isbetween 500 and 600 nm. In one embodiment, the final layer thickness isbetween 600 and 700 nm. In one embodiment, the final layer thickness isbetween 700 and 800 nm. In one embodiment, the final layer thickness isbetween 800 and 900 nm. In one embodiment, the final layer thickness isbetween 900 and 1000 nm. In one embodiment, the final layer thickness isbetween 1000 and 2000 nm. In one embodiment, the final layer thicknessis between 2000 and 3000 nm. In one embodiment, the final layerthickness is between 3000 and 4000 nm. In one embodiment, the finallayer thickness is between 4000 and 5000 nm. In one embodiment, thefinal layer thickness is between 5000 and 6000 nm. In one embodiment,the final layer thickness is between 6000 and 7000 nm. In oneembodiment, the final layer thickness is between 7000 and 8000 nm. Inone embodiment, the final layer thickness is between 8000 and 9000 nm.In one embodiment, the final layer thickness is between 9000 and 10000nm.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Examples 1-10

These examples illustrate the preparation of compounds G1 through G12.The solution photoluminescence data for these compounds is given inTable 2.

Example 1

This example demonstrates the preparation of an intermediate secondaryamine compounds.

(a) Amine 1:

21.2 g of 4-bromo-t-butylbenzene (100 mM) and 13.5 g (100 mM)4-i-propylaniline were mixed in a 500 mL flask in a nitrogen atmosphereglove

box. 1.0 g Pd₂ DBA₃ (1.08 mM), 0.44 g P(t-Bu)₃ (2.16 mM) and 10.6 gt-BuONa (110 mM) were added and all dissolved into 250 mL dry toluene.Upon addition of the Pd catalyst materials there is a sharp exotherm.Heat in glove box in mantle at 80° C. for 3 hrs then at room temp undernitrogen overnight. Cool and work up by silica chromatography(hexanes:toluene 1:1) product runs between starting materials) togenerate the secondary amine.

The product was collected as an off-white crystalline solid (˜21 g) fromethanol/water. The structure was confirmed by 1-H nmr analysis.

(b) Amine 2 was prepared in a similar fashion using 4-fluoroaniline and4-fluoro-bromobenzene

(c) Amine 3 was prepared in a similar fashion using 4-aminobiphenyl and4-bromobiphenyl

(d) Amine 4 was prepared in a similar fashion using 4-t-butylaniline and4-(3-biphenyl)-bromobenzene

(e) Amine 5 was prepared in a similar fashion using 4-t-butylaniline and4-bromobiphenyl

Example 2

This example demonstrates the preparation of Compounds G1 and G2.

3.34 g of dibromoanthracene (10 mM, Aldrich) and 5.4 g (21 mM)4-i-propyl,4-t-butylaniline (Amine 1) were mixed into 50 mL dry toluenein a

nitrogen-filled glove box. 1.0 g Pd₂ DBA₃ (1.0 mM), 0.41 g P(t-Bu)₃ (2.0mM) and 2.4 g t-BuONa (24 mM) were all dissolved into 50 mL toluene andadded to the reaction flask. The resulting slurry was stirred and heatedin the glove box in a mantle at 80° C. under nitrogen overnight. Thesolution is immediately dark purple but on reaching ˜80° C. it is darkyellow-green with noticeable green photoluminescence. The resultingsolution was cooled and removed from the glove box and filtered throughan alumina plug eluting with methylene chloride.

After filtration through the alumina pad and rinsing with methylenechloride, the deep green solution was evaporated to low volume. Yellowmicrocrystals begin to form and addition of methanol precipitated ayellow powdery material. Filtration and washing with methanol yields 6.5g of yellow microcrystals. Analysis by 1-H nmr in CDCl₃ confirmed thedesired product. The material was sublimed under high vacuum prior toevaluation in devices.

Compound G2 was made in an analogous manner, starting with9,10-dibromo-2-t-butylanthracene in place of 9,10-dibromoanthracene.

Example 3

This example demonstrates the preparation of Compound G3.

Step 1: t-butylation of anthracene

7.13 g (40 mM) anthracene and 10.8 g t-butanol (120 mM) were mixed in 40mL trifluoroacetic acid and refluxed for 15 hrs with vigorous stirring.The cooled solution was then poured into 300 mL ice cold water and theresulting ppt was collected by filtration. The off white solid was driedin vacuum and then recrystallized from hot toluene/methanol to yield ˜8g colorless crystals (˜70% yield) whose identity as2,6-di-t-butylanthracene was confirmed by nmr.

Step 2: bromination of 2,6-di-t-butylanthracene

4.94 g (17 mM) 2,6-di-t-butylanthracene was dissolved into 100 mL carbontetrachloride and 1.76 mL bromine (34 mM) was added dropwise withstirring at room temperature and the resulting mixture was stirred atroom temperature for 4 hrs. The pale orange solution was poured intowater and excess sodium sulfite to added consume any remaining bromine.The organic phase was collected and combined with methylene chlorideused to extract the aqueous layer. The organic layers were dried overanhydrous magnesium sulfate and then evaporated. The recovered solid wasrecrystallized from hot ethanol. The recovered yellow solid was furtherrecrystallized from methylene chloride/methanol to give ˜4.9 g of paleyellow crystals whose identity was confirmed by 1-H nmr.

Step 3: Amination of the dibromoanthracene

The procedure used for compound G1 described in Example 2 above wasfollowed using the 9,10-dibromo-2,6-di-t-butylanthracene from step 2 inplace of 9,10-dibromoanthracene.

This material appeared to be sparingly soluble in toluene and methylenechloride so was extracted by soxhlet using methylene chloride.Evaporation of the dark green solution generated bright yellowmicrocrystals which were intensely green luminescent. Soxhlet extractedmaterial gives ˜5.7 g of yellow microcrystals. 1-H nmr in CD₂Cl₂confirmed the identity of the material which was further purified bysublimation prior to device evaluation.

Example 4

This example demonstrates the preparation and separation of compounds G4and G5 which were made in an analogous manner to compound G3, startingwith 1-methylcyclohexanol in place of t-butanol in step 1.

Anthracene (10 g, 56 mmol) and trifluoroacetic acid (TFA) (56 mL) weretaken in a three neck round bottom flask, equipped with a stir-bar,reflux condenser and a dropping funnel containing methylcylohexanol(19.25 g, 168 mmol). The resulting slurry was brought to reflux undernitrogen and methylcylohexanol added to it in ˜5 ml batches over aperiod of 6 h. The reaction mixture turned purple-brown after the firstaddition and the reaction temperature (oil bath) was raised to 110° C.The reaction was stirred vigorously overnight and an additionalequivalent of methylcyclohexanol (6.41 g, 56 mmol) was added over aperiod of 30 min and the reaction allowed to reflux another 24 h. GC-MSshowed completed reaction, and no anthracene or mono-alkylated product,therefore the reaction mixture was cooled and filtered to remove TFA.The brownish solid residue was washed with ether until the filtrate ranclear (˜250 mL). The resulting pale yellow product (15.8 g, 76%) wascollected and considered pure enough by GC-MS and 1-H nmr for furtheruse. 1-H nmr clearly showed the presence of both 2,6- and 2,7-alkylatedisomers with the latter being the minor product.

Methylcyclohexylanthracene (14 g, 37.8 mmol) from the previous step andcarbontetrachloride (190 ml) were taken in a round bottom flask,equipped with a stir bar and a dropping funnel containing bromine (12 g,75.6 mmol) under nitrogen. Bromine was added dropwise to the stirredslurry over a period of 3 h until the solution became clear and GC-MSshowed no more starting material. The reaction was allowed to stir foranother hour and excess Bromine neutralized with a solution of Na₂S₂O₃.The two layers were separated and the aqueous layer extracted with 2×50ml CCl₄. The combined organic layers were dried (anhyd MgSO₄) andconcentrated to give a yellow solid which was stirred in refluxing EtOHfor 30 min and the resulting slurry allowed to cool over night. Theresulting pale yellow solid was collected by filtration and dried undervacuum to yield 18.5 g (92.6%) of the desired brominated compound as amixture of 2,6- and 2,7-alkylated products.

9-10-Dibromo-dimethylcyclohexylanthracene (18 g, 34 mmol) and4-tert-butyl-N-(4-isopropylphenyl)benzenamine (19.1 g, 71.5 mmol) weretaken in a 1 L round-bottom flask under nitrogen and 200 ml of drydegassed toluene was added to the flask yielding a yellow slurry. A 40ml vial was charged with Pd₂(dba)₃ (0.3 g, 0.3 mmol), P(^(t-)Bu)₃ (0.14g, 0.7 mmol) and 15 ml of dry toluene and left to stir in the glove box.After ten minutes, its contents were added to the reaction flask. Afterfurther ten minutes of stirring, sodium tert-butoxide (7.9 g, 81.8 mmol)was added in portions to the reaction flask under nitrogen and thereaction warmed in an 80° C. sand bath overnight. CL-LCMS showed thatthe reaction had not gone to completion therefore reaction was cooledand another batch of Pd₂(dba)₃ (1.25 g, 1.4 mmol) and P(^(t-)Bu)₃ (0.55g, 2.7 mmol) was added to it and the stirring continued over night.Reaction mixture was filtered through a 2+2″ plug of silica+celite andwashed with toluene and DCM until the flow through became clear.Filtrate was concentrated under reduced pressure resulting in darkyellow oil which yielded a yellow powder on standing. The powder wascollected by filtration and washed with ether to yield a first crop of10.82 g (35%) G4. nmr showed that the concentrated filtrate containedboth G4 and G5. A second precipitation yielded 11.22 g (36.5%) ofapproximately equal amounts G4 and G5 product and extremely dirty brownmaterial containing mostly G5 and other impurities. This last waspurified by silica gel chromatography using 1:15 DCM:hexane as theeluent to yield 3.8 g (12.4%) of predominantly G5 (73%).

Example 5

This example demonstrates the preparation of Compound G6.

2,6-dihydroxyanthraquinone (50 g, 0.2082 mol), sodium carbonate (35.0 g,0.3302 mol), and o-dichlorobenzene (800 mL) were combined in a 2 L flaskwith magnetic stirring, a water cooled condenser, and with N₂blanketing. Methyl-p-toluenesulfonate (110.0 g, 0.5907 mol) was addedover 20 minutes and the mixture heated to 178° C. overnight. The slurrywas cooled to 70° C. and added to 1 L of water. The mixture was filteredand the filter cake washed with water and methanol and dried to yield43.8 g of a light tan solid for a 78% yield.

Combined 2,6-dimethoxyanthraquinone (16.7 g, 0.0623 mol) from step 1above with 1250 mL isopropyl alcohol and degassed with nitrogen for 30minutes. Added NaBH₄ (49 g, 1.295 mol) and refluxed overnight. Cooledand evaporated solvent and added 500 mL of iced water followed by 135 gof conc. HCl in portions until pH<2. Extracted aqueous mixture withdichloromethane and concentrated to 13.31 g of black solid which waspreabsorbed onto 61 g of silica and purified by silica columnchromatography eluting with hexanes and dichloromethane thenrecrystallized from chloroform yielding 1.58 g of product. The motherliquor material was purified by silica column chromatography again toyield another 1.28 g of product for a total yield of 19%

2,6-dimethoxyanthracene (2.49 g, 0.0105 mol), and 114 mL of carbontetrachloride were combined and bromine (3.78 g, 0.0237 mol) in portionsuntil no change was detected by nmr. The mixture was diluted with 700 mLdichloromethane and washed with 200 mL water and Na₂S₂O₄ (11 g, 0.0696mol). Organics were separated, concentrated and purified by columnchromatography. Well purified material totaled 0.3 g yielding 7% butimpure material needing further purification totaled 2.18 g for a crudeyield of 45%

Combined 4-t-butyl-4′-isopropyldiphenylamine (0.421 g, 0.0016 mol),2,6-dimethoxy-9,10-dibromoanthracene (0.2495 g, 0.00063 mol), Pd₂ DBA₃(0.0419 g, 0.0457 mmol), tri-t-butylphosphine (0.0185 g, 0.0914 mmol),sodium t-butoxide (0.1211 g, 1.26 mmol), and 8 mL toluene. Ran at 95° C.over 50 hours. Purified by column chromatography on basic-alumina thenprecipitation from dichloromethane with acetonitrile to yield 100 mg ofpure material for a 20% yield.

Example 6

This example demonstrates the preparation of Compounds G7 and G8.

The two isomers of the bis-1-adamantyl anthracene were prepared in ananalogous manner to those of G4 and G5 above using 1-adamantanol inplace of 1-methylcyclohexanol. Separation of the G7 from the G8 isomeris best achieved by separation of the initial products of alkylationprior to the bromination step. The 2,7-bis-1-adamantyl anthracene (theisomer leading to G8) being the more soluble material and so extractionwith toluene at this stage leaves behind the 2,6 isomer and provides asolution of the 2,7 isomer. Subsequent recrystallization from methylenechloride of the isolated solids further purifies each individual isomer.The final G7 and G8 materials are both quite soluble in toluene and werefurther purified by sublimation prior to device evaluation. 1-H nmrspectroscopy identified the individual materials and confirmed theirisomeric assignments:

Example 7

This example demonstrates the preparation of compound G9

2.25 g of the 9,10-dibromo-2,6-di-t-butyl-anthracene (5 mM) and 2.25 g(11 mM) amine 2 were mixed in 25 mL toluene in a nitrogen glove box. 0.5g Pd₂ DBA₃ (0.5 mM), 0.20 g tri-t-butylphosphine (1 mM) and 1.0 gt-BuONa (20 mM) were mixed and dissolved into 10 mL toluene. Then twosolutions were mixed and heated in the glove box at 80° C. for 1 hr thenwarmed gently (˜50° C.) under nitrogen overnight. The mixed solution isimmediately dark purple but on reaching 80° C. it becomes darkyellow-brown. The solution is cooled, removed from the glove box andfiltered through an alumina plug eluting with methylene chloride. TLC ofthe light yellow filtrate shows a bright green photoluminescent spot.Further purification on Florisil eluting with methylene chloridecollected a bright yellow solution (with visible green photoluminescencein room light) which crystallized on addition of methanol and standingo/n. Final recrystallization from toluene by addition of methanolyielded ˜2.5 g bright yellow crystals. The yellow solid was identifiedas the desired compound (wet with a little toluene) by 1-H nmr and thenfurther purified by train sublimation prior to device evaluation.

Example 8

This example demonstrates the preparation of compound G10

0.94 g of the 9,10-dibromo-2,6-di-(1-adamantyl)-anthracene (1.5 mM) (seeExample 6 above) and 1.0 g (3.1 mM) amine 3 were mixed in 10 mL toluenein a nitrogen glove box. 0.15 g Pd₂ DBA₃ (0.15 mM), 0.06 gtri-t-butylphosphine (0.3 mM) and 0.32 g t-BuONa (3.3 mM) were mixed anddissolved into 10 mL toluene. Then two solutions were mixed and heatedin the glove box at 80° C. for 1 hr then warmed gently (˜50° C.) undernitrogen overnight. The mixed solution is immediately dark purple but onreaching 80° C. it becomes dark yellow-brown. The solution is cooled,removed from the glove box and filtered through an alumina plug elutingwith methylene chloride. TLC of the light yellow filtrate shows a brightgreen photoluminescent spot. Further purification on FLORISIL elutingwith methylene chloride collected a bright yellow solution (with visiblegreen photoluminescence in room light) which crystallized on addition ofmethanol. Final recrystallization from toluene yielded ˜1.1 g brightyellow crystals. The yellow solid was identified as the desired compound(wet with a little toluene) by 1-H nmr and then further purified bytrain sublimation prior to device evaluation.

Example 9

This example demonstrates the preparation of compound G11

3.02 g of the 9,10-dibromo-2,6-di-(1-adamantyl)-anthracene (5 mM) (seeExample 6 above) and 3.85 g (11 mM) amine 4 were mixed in 25 mL toluenein a nitrogen glove box. 0.5 g Pd₂ DBA₃ (0.5 mM), 0.20 gtri-t-butylphosphine (1 mM) and 1.0 g t-BuONa (20 mM) were mixed anddissolved into 10 mL toluene. Then two solutions were mixed and heatedin the glove box at 80° C. for 1 hr then warmed gently (˜50° C.) undernitrogen overnight. The mixed solution is immediately dark purple but onreaching 80° C. it becomes dark yellow-brown. The solution is cooled,removed from the glove box and filtered through an alumina plug elutingwith methylene chloride. TLC of the deep orange filtrate shows a brightgreen photoluminescent spot. Further purification on FLORISIL and thenon neutral alumina eluting with methylene chloride collected a brightyellow solution (with visible green photoluminescence in room light)which crystallized on addition of methanol and standing o/n. Finalrecrystallization from toluene by addition of methanol yielded ˜2.2 gbright yellow crystals. The yellow solid was identified as the desiredcompound (wet with a little toluene and methanol) by 1-H nmr and thenfurther purified by train sublimation prior to device evaluation.

Example 10

This example demonstrates the preparation of compound G12

0.25 g of the 9,10-dibromo-2,6-di-(1-adamantyl)-anthracene (0.42 mM)(see Example 6 above) and 0.3 g (1 mM) amine 5 were mixed in 10 mLtoluene in a nitrogen glove box. 0.04 g Pd₂ DBA₃ (0.04 mM), 0.017 gtri-t-butylphosphine (0.08 mM) and 0.1 g t-BuONa (1 mM) were mixed anddissolved into 10 mL toluene. Then two solutions were mixed and heatedin the glove box at 80° C. for 1 hr then warmed gently (˜50° C.) undernitrogen overnight. The mixed solution is immediately dark purple but onreaching 80° C. it becomes dark yellow-brown. The solution was cooled,removed from the glove box and filtered through an alumina plug elutingwith methylene chloride. TLC of the deep yellow filtrate shows a brightgreen photoluminescent spot. Further purification on FLORISIL and thenneutral alumina eluting with methylene chloride collected a brightyellow solution (with visible green photoluminescence in room light)which crystallized on addition of methanol and standing o/n. Finalrecrystallization from toluene by addition of methanol yielded ˜0.24 gbright yellow crystals. The yellow solid was identified as the desiredcompound (wet with a little toluene and methanol) by 1-H nmr and thenfurther purified by train sublimation prior to device evaluation.

TABLE 2 Solution Photoluminescence and Color Solution Solution SolutionCompound PL CIE x CIE y control 528.5 0.306 0.662 G1 532 0.327 0.650 G2528.5 0.305 0.664 G3 524.5 0.289 0.667 G4 524 0.278 0.673 G5 518.5 0.2470.657 G6 522.5 0.280 0.659 G7 526 0.290 0.669 G8 521.5 0.265 0.658 G9508 0.212 0.657 G10 520 0.25 0.659 G11 519 0.244 0.649 G12 518 0.2470.657 control =2-t-butyl-N,N,N′,N′-tetra-p-tolyl-anthracene-9,10-diamine PL =photoluminescence maximum, in nm CIE x and y refer to the colorcoordinates according to the C.I.E. chromaticity scale (CommisionInternationale de L'Eclairage, 1931)

Example 11

This example demonstrates the preparation of hole transport materialHT1.

(a) Synthesis of Compound 11-2

Under an atmosphere of nitrogen, a 250 mL round bottom was charged with9,9-dioctyl-2,7-dibromofluorene (25.0 g, 45.58 mmol), phenylboronic acid(12.23 g, 100.28 mmol), Pd₂(dba)₃ (0.42 g, 0.46 mmol), P^(t)Bu₃ (0.22 g,1.09 mmol) and 100 mL toluene. The reaction mixture stirred for fiveminutes after which KF (8.74 g, 150.43 mmol) was added in two portionsand the resulting solution was stirred at room temperature overnight.The mixture was diluted with 500 mL THF and filtered through a plug ofsilica and celite and the volatiles were removed from the filtrate underreduced pressure. The yellow oil was purified by flash columnchromatography on silica gel using hexanes as eluent. The product wasobtained as a white solid in 80.0% yield (19.8 g). The structure wasconfirmed by 1-H nmr analysis.

(b) Synthesis of Compound 11-3

A 250 mL three-necked-round-bottom-flask, equipped with a condenser anddripping funnel was flushed with N₂ for 30 minutes.9,9-dioctyl-2,7-diphenylfluorene (19.8 g, 36.48 mmol) (compound 11-2above) was added and dissolved in 100 mL dichloromethane. The clearsolution was cooled to −10° C. and a solution of bromine (12.24 g, 76.60mmol) in 20 mL dichloromethane was added dropwise. The mixture wasstirred for one hour at 0° C. and then allowed to warm to roomtemperature and stirred overnight. 100 mL of an aqueous 10% Na₂S₂O₃solution was added and the reaction mixture was stirred for one hour.The organic layer was extracted and the water layer was washed threetimes with 100 mL dichloromethane. The combined organic layers weredried with Na₂SO₄ filtered and concentrated to dryness. Addition ofacetone to the resulting oil gave a white precipitated. Upon filtrationand drying a white powder was obtained (13.3 g, 52.2%). The structurewas confirmed by 1-H nmr analysis.

(c) Synthesis of Compound 11-4

Under an atmosphere of nitrogen, a 250 mL round bottom was charged withcompound 11-3 (13.1 g, 18.70 mmol), aniline (3.66 g, 39.27 mmol),Pd₂(dba)₃ (0.34 g, 0.37 mmol), P^(t)Bu₃ (0.15 g, 0.75 mmol) and 100 mLtoluene. The reaction mixture stirred for 10 min after which NaOtBu(3.68 g, 38.33 mmol) was added and the reaction mixture was stirred atroom temperature for one day. The resulting reaction mixture was dilutedwith 3 L toluene and filtered through a plug of silica and celite. Uponevaporation of volatiles, the dark brown oil obtained was purified byflash column chromatography on silica gel using a mixture of 1:10 ethylacetate:hexanes as eluent. The product was obtained as a pale yellowpowder in 50.2% yield (6.8 g). The structure was confirmed by 1-H nmranalysis.

(d) Synthesis of Compound 11-5

In a 250 mL three-necked-round-bottom-flask equipped with condenser,compound 11-4 (4.00 g, 5.52 mmol), 1-bromo-4-iodobenzene (4.68 g, 16.55mmol), Pd₂(dba)₃ (0.30 g, 0.33 mmol) and DPPF (0.37 g, 0.66 mmol) werecombined with 80 mL toluene. The resultant mixture was stirred for 10min. NaOtBu (1.17 g, 12.14 mmol) was added and the mixture was heated to80° C. for four days. The resulting reaction mixture was diluted with 1L toluene and 1 L THF filtered through a plug of silica and celite toremove the insoluble salts. Upon evaporation of volatiles, the resultingbrown oil was purified by flash column chromatography on silica gelusing a mixture of 1:10 dichloromethane:hexanes as eluent. After dryinga yellow powder was obtained (4.8 g, 84.8%). The structure was confirmedby 1-H nmr analysis.

(e) Synthesis of Compound 11-6

This compound was made according to the procedure published in Klaerner,G.; Lee, J.-I.; Lee, V. Y.; Chan, E.; Chen, J.-P.; Nelson, A.;Markiewicz, D.; Siemens, R.; Scott, J. C.; Miller, R. D., Chemistry ofMaterials (1999), 11 (7), 1800-1805.

(f) Synthesis of HT1

Bis(1,5-Cyclooctadiene)-nickel-(0) (0.556 g, 2.02 mmol) was added to aN,N-dimethylformamide (anhydrous, 4 mL) solution 2,2′-bipyridyl (0.0.315g, 2.02 mmol) and 1,5-cyclooctadiene (0.219 g, 2.02 mmol). The resultingmixture was heated to 60° C. for 30 min. A toluene (anhydrous, 16 mL)solution of 2,7-dibromo-9,9′-(p-vinylbenzyl)-fluorene (0.0834 g, 0.15mmol) and compound 11-5 (0.88 g, 0.85 mmol), was then added rapidly tothe stirring catalyst mixture. The mixture was stirred at 60° C. forseven hours. After the reaction mixture cooled to room temperature, itwas poured, slowly, with vigorous stirring into 250 mL methanol andstirred overnight. Addition of 15 mL of conc. HCl followed and stirringfor an hour. The precipitate was filtered and then added to 50 mL oftoluene and poured slowly into 500 mL of methanol. The resultinglight-yellow precipitate was stirred for one hour and then isolated byfiltration. The solid was further purified by chromatography (silica,toluene) and precipitation from ethyl acetate. After drying theresulting material under vacuum a light yellow polymer was isolated in80% yield (0.64 g). GPC (THF, room temperature): Mn=80,147; Mw=262,659;Mw/Mn=2.98.

Example 12

This example demonstrates the preparation of host material H1.

H1 was prepared according to the following scheme:

(a) Synthesis of Compound 12-2

Compound 12-22 was synthesized following the procedure in US applicationpublication 2005/0245752.

(b) Synthesis of Compound 12-3

Amount MW Relative Compound Amount (g) (mol) (g/mol) Equivalentsanthracen-9-yl 10.0 0.0306 326.29 1.00 trifluoromethanesulfonateNapthalen-2-yl-boronic 6.33 0.0368 171.99 1.20 acid Potassium phosphate29.2 0.137 212.27 4.5 tribasic Palladium(II) acetate 0.687 0.00306224.51 0.10 tricyclohexylphosphine 0.858 0.00306 280.43 0.10tetrahydrofuran 75 mL Water 45 mL 18.02 9-(naphthalen-2- 9.31 0.0306304.38 1.00 yl)anthracene (theoretical)All solid reagents and THF were combined in a 200 mL Kjeldahl reactionflask equipped with a stir bar in a nitrogen-filled glove box. Afterremoval from the dry box, the reaction mixture was purged with nitrogenand degassed water was added by syringe. A condenser was then added andthe reaction was refluxed for 24 hours. TLC was performed indicating theabsence of the anthracen-9-yl trifluoromethanesulfonate startingmaterial. After cooling the organic layer was separated and the aqueouslayer was extracted with DCM. The organic fractions were combined andthe solvent was removed under reduced pressure. The resulting crudesolid was purified by column chromatography using Aldrich neutralalumina and 5% DCM in hexanes. The solvent polarity was increasedgradually to 50% DCM. Solvent removal gave 4.08 g of a white solid(43.8% yield). The product was confirmed by 1-H nmr analysis.

(c) Synthesis of Compound 12-4

(d) Synthesis of Compound 12-5

Amount MW Relative Compound Amount (g) (mol) (g/mol) Equivalentsnaphthalen-1-yl-1- 14.20 0.0826 171.99 1.00 boronic acid1-bromo-4-iodobenzene 25.8 0.0912 282.9 1.10 Tetrakis 1.2 0.001381155.56 0.0126 (triphenylphospine) palladium(0) sodium carbonate 25.40.24 105.99 2.90 toluene 200 mL water 120 mL 1-(4-bromophenyl)- 23.40.0826 283.16 1.00 naphthalene (theoretical)All reagents and toluene were combined in a 500 mL round bottom flaskequipped with a stir bar in a nitrogen-filled glove box. After removalfrom the dry box, the reaction mixture was purged with nitrogen anddegassed water was added by syringe. A condenser was equipped and thereaction was refluxed for 15 hours. TLC was performed indicating thereaction was complete. The reaction mixture was cooled to roomtemperature. The organic layer was separated and the aqueous layer wasextracted with DCM. The organic fractions were combined and the solventwas removed under reduced pressure to give a viscous oil. The crudematerial was purified by column chromatography using silica gel and 10%DCM/Hexanes. Solvent removal gave 20 grams (85% yield) of a clear,viscous oil. The product was confirmed by 1-H nmr analysis.

(e) Synthesis of Compound 12-6

To a solution of 1-(4-bromo-phenyl)-naphthalene (40 g) dissolved inanhydrous THF (800 mL), was added slowly of nBuLi (1.6 M in hexane, 130mL) at −78° C. (dry ice/acetone). The reaction mixture turned brown andwas stirred for 10 min at −78° C. then warmed up, stirred for further 10min and then cooled back down to −78° C. To this was added dioxaborolane(42.8 mL) and the reaction stirred at this temperature for 0.5 h beforewarming to room temperature and stirring for 1 hour. Water was thenadded to the reaction mixture which was thoroughly, extracted with Et₂O.The organic layers were dried over anhydrous magnesium sulfate andfiltered. The solvents were removed under vacuum and water was addedinto this concentrated solution, a white solid was formed and filtered.The crude product was recrystallized in toluene, dried under vacuum toyield 25 g of 12-6 as a white solid.

(f) Synthesis of H1

Amount MW Relative Compound Amount (g) (mol) (g/mol) Equivalents10-bromo-9- 1.00 0.00261 383.28 1.00 (naphthalen-7- yl)anthracene4,4,5,5-tetramethyl- 0.95 0.0029 330.23 1.10 2-(4-(naphthalen-4-yl)phenyl)- 1,3,2- dioxaborolane Tetrakis- 0.15 0.00013 1155.56 0.05triphenylphosphine palladium (0) Sodium carbonate 5.3 0.050 105.99 THF25 mL Water 25 mL 10-(4-(naphthalen- 1.32 506.63 1-yl)phenyl)-9-(theoretical) (naphthalen-7- yl)anthraceneAll reagents and THF were combined in a 100 mL round bottom flaskequipped with a stir bar in a nitrogen-filled glove box. After removalfrom the dry box, the reaction mixture was purged with nitrogen anddegassed water was added by syringe. A condenser was equipped and thereaction was refluxed for 72 hours. LC-MS was performed indicating thereaction was complete. The reaction mixture was cooled to roomtemperature. The organic layer was separated and the aqueous layer wasextracted with DCM. The organic fractions were combined and the solventwas removed under reduced pressure to give a grey solid. The crudematerial was purified by column chromatography using silica gel andDCM/Hexanes. Solvent removal gave 1 gram (76% yield) as a white solid.Host H1 was purified using both solution and vapor sublimationtechniques.

Example 13

This example illustrates the preparation of host H2.

Host material H2 was synthesized in an analogous manner to H1 followingthe Scheme below.

(a) Synthesis of Compound 13-1

To a mixture of4,4,5,5-tetramethyl-2-(4-naphthalen-1-yl-phenyl[1,3,2]dioxaborolane(20.7 g) and 9-bromo-anthracene (14.6 g) in toluene (300 ml) was added2M sodium carbonate (12.1 g dissolved in 57 ml of water) followed by theaddition of phase-transfer agent Aliquat336 (2.4 g). The mixture wasbubbled with nitrogen for 15 min before addition oftetrakis(triphenylphosphine)palladium(0) (Pd[(C₆H₅)₃P]₄, (0.69 g) andthe reaction was heated at 90° C. (oil bath) for one day under anitrogen atmosphere. The reaction mixture was then cooled to roomtemperature, extracted with ethyl ether. The organic solvent was removedunder vacuum and the crude product was washed with hexane, purified by ashort column of FLORISIL using hexane:THF (1:1.5) as an eluent. To yield17 g of the desired compound as a white solid.

(b) Synthesis of Compound 13-2

9-(4-naphthalen-1-yl-phenyl)-anthracene (15 g, 40 mmol) was dissolvedinto methylene chloride (500 ml) in a 3-necks round bottom flask andbromine (7 g, d 3.12 g/ml, FW 159.81, 44 mmol) was added slowly via adropping funnel over a period of 1 hour. The reaction mixture is thensparged with nitrogen to remove HBr and the reaction stirred overnightat room temperature. The reaction mixture was then extracted with water,dried over MgSO₄, and filtered over FLORISIL. The solvent was removedunder vacuum and a yellow solid was collected which on washing withhexane and drying yielded 16 g of yellow solid as the desired compound.

(c) Synthesis of Compound H2

To a mixture of4,4,5,5-tetramethyl-2-(4-naphthalen-2-yl-phenyl)-[1,3,2]dioxaborolane(12.6 g) and 9-bromo-10-(4-naphthalen-1-yl-phenyl)-anthracene (16 g) intoluene (300 ml) was added 2M sodium carbonate (7.4 g dissolved in 35 mlof water) followed by the addition of phase-transfer agent Aliquat336(1.4 g). The mixture was bubbled with nitrogen for 15 min beforeaddition of tetrakis(triphenylphosphine)palladium(0) (Pd[(C₆H₅)₃P]₄,(0.40 g) and the reaction was heated at 90° C. (oil bath) for one dayunder a nitrogen atmosphere. The reaction mixture was then cooled toroom temperature, extracted with ethyl ether, dried over MgSO₄, filteredand added into methanol, filtered and the yellow solid so collecteddried under vacuum. The yellow solid was dissolved in THF, passedthrough FLOROSIL column with THF/hexane (1:1), concentrated under vacuumto yield 10 g light yellow solid which was purified by 3-zone (250 C,210 C, 170 C) sublimation for 70 hours. 5.6 g pale yellow solid wasrecovered.

Examples 14-27

These examples demonstrate the fabrication and performance of organicelectronic devices having green emission.

Device Fabrication and Testing

The devices were constructed as follows:

Indium Tin Oxide (ITO): 100 nm

buffer layer=Buffer 25 nm), which is an aqueous dispersion ofpolypyrrole and a polymeric fluorinated sulfonic acid. The material wasprepared using a procedure similar to that described in Example 1 ofpublished U.S. patent application no. 2005/0205860.

hole transport layer=polymer HT1 (20 nm)

photoactive layer=13:1 host:dopant (48 nm)

electron transport (ET) layer=(20 nm)

cathode=LiF/Al (0.5/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 30 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Immediately before device fabrication the cleaned, patterned ITOsubstrates were treated with UV ozone for 10 minutes. Immediately aftercooling, an aqueous dispersion of Buffer 1 was spin-coated over the ITOsurface and heated to remove solvent. After cooling, the substrates werethen spin-coated with a solution of a hole transport material, and thenheated to remove solvent. After cooling the substrates were spin-coatedwith the emissive layer solution, and heated to remove solvent. Thesubstrates were masked and placed in a vacuum chamber. An electrontransport layer was deposited by thermal evaporation, followed by alayer of LiF. Masks were then changed in vacuo and a layer of Al wasdeposited by thermal evaporation. The chamber was vented, and thedevices were encapsulated using a glass lid, dessicant, and UV curableepoxy.

The OLED samples were characterized by measuring their (1)current-voltage (I-V) curves, (2) electroluminescence radiance versusvoltage, and (3) electroluminescence spectra versus voltage. All threemeasurements were performed at the same time and controlled by acomputer. The current efficiency of the device at a certain voltage isdetermined by dividing the electroluminescence radiance of the LED bythe current density needed to run the device. The unit is a cd/A. Thepower efficiency is the current efficiency divided by the operatingvoltage. The unit is Im/W.

The materials used (host, dopant, and ET material) are given in Table 3.The device results are given in Table 4. For comparison, a controldopant was used.

control dopant=2-t-butyl-N,N,N′,N′-tetra-p-tolyl-anthracene-9,10-diamine

AlQ=tris(8-hydroxyquinolato)aluminum

ZrQ=tetrakis(8-hydroxyquinolato)zirconium

TABLE 3 Device Materials Example Dopant Host ET control control dopantH1 AIQ 14 G1 H1 AIQ 15 G2 H1 ZrQ 16 G3 H1 ZrQ 17 G4 H1 ZrQ 18 G4 H2 ZrQ19 G4:G5 (1:1) H2 ZrQ 20 G6 H2 ZrQ 21 G7 H2 ZrQ 22 G7:G8 (1:1) H2 ZrQ 23G8 H2 ZrQ 24 G9 H2 ZrQ 25 G10 H2 ZrQ 26 G11 H2 ZrQ 27 G12 H2 ZrQ

TABLE 4 Device Results CE Voltage Lum. ½ EL EL EL Example [cd/A] (V)Life [h] peak CIE x CIE y Control 15.2 4.3 135,000 530 0.310 0.644 1413.5 4.3 143,000 532 0.314 0.640 15 20.8 4.3 132,000 528 0.294 0.651 1622.8 4.3 140,000 525.5 0.288 0.648 17 23.2 4.3 126,000 524 0.275 0.65218 22.5 4.2 171,000 524 0.280 0.653 19 21.4 4.6 120,000 524 0.291 0.64720 20.7 4.3 36,500 524.5 0.290 0.635 21 19.9 4.2 106,000 526 0.287 0.65122 23.8 4.2 223,000 527 0.291 0.651 23 21.5 4.5 165,000 527.7 0.2930.648 24 12.3 4.6 10,700 515 0.252 0.621 25 19.3 4.3 250,000 526 0.2990.646 26 17.7 4.3 14,000 528 0.291 0.645 27 17.2 4.3 205,000 528 0.2950.645 * All data @ 1000 nits, CE = current efficiency; Lum. ½ Life =time to reach ½ of initial luminance, in hours; CIE x and y refer to thecolor coordinates according to the C.I.E. chromaticity scale (CommisionInternationale de L'Eclairage, 1931)

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

The use of numerical values in the various ranges specified herein isstated as approximations as though the minimum and maximum values withinthe stated ranges were both being preceded by the word “about.” In thismanner slight variations above and below the stated ranges can be usedto achieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum average valuesincluding fractional values that can result when some of components ofone value are mixed with those of different value. Moreover, whenbroader and narrower ranges are disclosed, it is within thecontemplation of this invention to match a minimum value from one rangewith a maximum value from another range and vice versa.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.

1. A green luminescent material having Formula I or Formula II

wherein: R¹ and R² are the same or different and are selected from thegroup consisting of hydrogen, alkoxy, tertiary alkyl, and cycloalkyl. R³and R⁴ are the same or different and are selected from the groupconsisting of fluorine, aryl, and alkyl.
 2. The luminescent material ofclaim 1, wherein at least one of R¹ and R² is not hydrogen.
 3. Theluminescent material of claim 1, wherein at least one of R¹ and R² is analkoxy group selected from the group consisting of methoxy and ethoxy.4. The luminescent material of claim 1, wherein at least one of R¹ andR² is a tertiary alkyl group selected from the group consisting oft-butyl and neopentyl.
 5. The luminescent material of claim 1, whereinat least one of R¹ and R² is a cycloalkyl selected from the groupconsisting of cyclohexyl, 1-methylcyclohexyl, and 1-adamantyl.
 6. Theluminescent material of claim 1, selected from the group consisting ofcompounds G1 through G12: Compound Formula R¹ R² R³ R⁴ G1 I H H i-propylt-butyl G2 I t-butyl H i-propyl t-butyl G3 I t-butyl t-butyl i-propylt-butyl G4 I 1- 1- i-propyl t-butyl methylcyclohexyl methylcyclohexyl G5II 1- 1- i-propyl t-butyl methylcyclohexyl methylcyclohexyl G6 I methoxymethoxy i-propyl t-butyl G7 I 1-adamantyl 1-adamantyl i-propyl t-butylG8 II 1-adamantyl 1-adamantyl i-propyl t-butyl G9 I t-butyl t-butyl F FG10 I 1-adamantyl 1-adamantyl phenyl phenyl G11 I 1-adamantyl1-adamantyl t-butyl 3-biphenyl G12 I 1-adamantyl 1-adamantyl t-butylphenyl


7. An organic electronic device comprising a first electrical contact, asecond electrical contact and a photoactive layer therebetween, thephotoactive layer comprising a green luminescent material having FormulaI or Formula II

wherein: R¹ and R² are the same or different and are selected from thegroup consisting of hydrogen, alkoxy, tertiary alkyl, and cycloalkyl. R³and R⁴ are the same or different and are selected from the groupconsisting of fluorine, aryl, and alkyl.
 8. The device of claim 7,wherein at least one of R¹ and R² is not hydrogen.
 9. The device ofclaim 7, wherein at least one of R¹ and R² is an alkoxy group selectedfrom the group consisting of methoxy and ethoxy.
 10. The device of claim7, wherein at least one of R¹ and R² is a tertiary alkyl group selectedfrom the group consisting of t-butyl and neopentyl.
 11. The device ofclaim 7, wherein at least one of R¹ and R² is a cycloalkyl selected fromthe group consisting of cyclohexyl, 1-methylcyclohexyl, and 1-adamantyl.12. The device of claim 7, wherein the luminescent material is selectedfrom the group consisting of compounds G1 through G12: Compound FormulaR¹ R² R³ R⁴ G1 I H H i-propyl t-butyl G2 I t-butyl H i-propyl t-butyl G3I t-butyl t-butyl i-propyl t-butyl G4 I 1- 1- i-propyl t-butylmethylcyclohexyl methylcyclohexyl G5 II 1- 1- i-propyl t-butylmethylcyclohexyl methylcyclohexyl G6 I methoxy methoxy i-propyl t-butylG7 I 1-adamantyl 1-adamantyl i-propyl t-butyl G8 II 1-adamantyl1-adamantyl i-propyl t-butyl G9 I t-butyl t-butyl F F G10 I 1-adamantyl1-adamantyl phenyl phenyl G11 I 1-adamantyl 1-adamantyl t-butyl3-biphenyl G12 I 1-adamantyl 1-adamantyl t-butyl phenyl


13. The device of claim 7, wherein the photoactive layer furthercomprises a host material.
 14. The device of claim 13 wherein the hostmaterial comprises at least one diarylanthracene.
 15. The device ofclaim 14 wherein the diarylanthracene has the formula:

where: A¹ and A² are the same or different at each occurrence and areselected from the group consisting of H, an aromatic group, and analkenyl group, or A may represent one or more fused aromatic rings; pand q are the same or different and are an integer from 1-3.
 16. Thedevice of claim 15 wherein at least one of A¹ and A² comprises anaphthyl group.
 17. The device of claim 16 wherein the host is selectedfrom the group consisting of

and combinations thereof.
 18. A photoactive layer comprising a greenluminescent material of claim
 1. 19. The photoactive layer of claim 18further comprising a host material comprising at least onediarylanthracene.